Substituted pyrazolines for use as pesticides

ABSTRACT

The present invention relates to novel substituted pyrazolines of formula (I)  
                 
 
in which R 1 , R 2 , R 3  and R 4  are as defined in the disclosure, to a plurality of processes for preparing these compounds and their use for controlling pests, and also to novel intermediates and processes for their preparation.

The present invention relates to novel substituted pyrazolines, toprocesses for their preparation and to their use as pesticides.

It is known that certain substituted pyrazolines have insecticidal andacaridical properties (cf., for example, DE-A 44 16 112, EP-A 0 679 644or EP-A 0 438 690). However, in particular at low concentrations ofactive compound and low application rates, the action of these compoundsis not always satisfactory.

This invention provides novel substituted pyrazolines of the formula (I)

in which

-   R¹ represents halogen or cyano,-   R² represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio,    haloalkylthio, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl    or cyano,-   R³ represents optionally substituted aryl or optionally substituted    hetaryl and-   R⁴ represents hydrogen, cyanomethyl or alkoxycarbonyl.

Depending on the nature and number of the substituents, the compounds ofthe formula (I) may be present as geometrical and/or optical isomers,regio isomers and/or configurational isomers or isomer mixtures thereofof varying composition. What is claimed by the invention are both thepure isomers and the isomer mixtures.

Furthermore, it has been found that the substituted pyrazolines of theformula (I) are obtained whena) pyrazolines of the formula (II)

in which

-   R¹ and R² are as defined above are reacted with isocyanates of the    formula (II)    in which-   R³ is as defined above, if appropriate in the presence of a diluent    and if appropriate in the presence of a catalyst;    and    b) the resulting pyrazoline derivatives of the formula (Ia)    according to the invention    in which-   R¹, R² and R³ are as defined above are optionally reacted with    halides of the formula (IV)    Hal¹-R  (IV)    in which-   R⁴ is as defined above and-   Hal¹ represents halogen,    if appropriate in the presence of a diluent and if appropriate in    the presence of a base; or    c) anilines of the formula (V)    in which-   R³ and R⁴ are as defined above are initially reacted with phosgene    in the presence of a diluent and if appropriate in the presence of a    base, and the resulting carbamoyl chlorides of the formula (VI)    in which-   R³ and R⁴ are as defined above are reacted directly or after    intermediate isolation with pyrazolines of the formula (II)    in which-   R¹ and R² are as defined above, in the presence of a diluent and if    appropriate in the presence of a base.

Finally, it has been found that the novel substituted pyrazolines of theformula (I) have pronounced biological properties and are suitableespecially for controlling animal pests, in particular insects,arachnids and nematodes, encountered in agriculture, in forests, in theprotection of stored goods and materials and in the hygiene sector.

The formula (I) provides a general definition of the pyrazolinederivatives according to the invention.

Preferred substituents or ranges of the radicals listed in the formulaeabove and below are illustrated below:

-   R¹ preferably represents fluorine, chlorine, bromine, iodine or    cyano.-   R² preferably represents fluorine, chlorine, bromine, iodine;    C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,    C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfinyl,    C₁-C₄-haloalkylsulfonyl or cyano.-   R³ preferably represents aryl which is optionally mono- or    polysubstituted by identical or different substituents, examples of    substituents which may be mentioned being: halogen, alkyl, alkoxy,    alkylthio, alkylsulfonyl, haloalkyl, haloalkoxy, haloalkylthio,    haloalkylsulfonyl or cyano;

represents in each case optionally monosubstituted oxadiazolyl orthiadiazolyl, examples of substituents which may be mentioned being:optionally substituted alkyl, optionally substituted alkoxy, optionallysubstituted alkylthio, optionally substituted aryl or optionallysubstituted arylalkyl;

represents optionally monosubstituted tetrazolyl, examples ofsubstituents which may be mentioned being: optionally substituted alkyl,optionally substituted alkylthio or alkylsulfonyl, in each caseoptionally substituted aryl or arylalkyl or optionally substitutedcycloalkyl.

-   R⁴ preferably represents hydrogen, cyanomethyl or    C₁-C₄-alkoxycarbonyl.-   R¹ particularly preferably represents chlorine, bromine, iodine or    cyano.-   R² particularly preferably represents fluorine, chlorine, bromine,    iodine, cyano, C₁-C₂-alkylthio, C₁-C₂-alkylsulfonyl, and also    represents C₁-C₂-haloalkyl, C-C₂-haloalkoxy, C₁-C₂-haloalkylthio or    C₁-C₂-haloalkylsulfonyl having in each case 1 to 5 identical or    different halogen atoms from the group consisting of fluorine,    chlorine and bromine.-   R³ particularly preferably represents phenyl which is optionally    mono- to trisubstituted by identical or different substituents,    examples of substituents which may be mentioned being: fluorine,    chlorine, bromine, iodine, cyano; C₁-C₄-alkyl, C₁-C₄-alkoxy,    C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, and also represents    C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio or    C₁-C₄-haloalkylsulfonyl having in each case 1 to 5 identical or    different halogen atoms from the group consisting of fluorine,    chlorine and bromine;

represents in each case optionally monosubstituted oxadiazolyl orthiadiazolyl, examples of substituents which may be mentioned being:C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, and also phenyl or benzyl, each ofwhich is optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, C₁-C₄-haloalkyl andC₁-C₄-haloalkoxy;

represents optionally substituted tetrazolyl, examples of substituentswhich may be mentioned being: C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, and also phenyl or benzyl, each ofwhich is optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, C₁-C₄-haloalkyl andC₁-C₄-haloalkoxy, furthermore cyclopentyl or cyclohexyl, each of whichis optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of C₁-C₄-alkyl.

-   R⁴ particularly preferably represents hydrogen, cyanomethyl or    C₁-C₄-alkoxycarbonyl.-   R¹ very particularly preferably represents chlorine, bromine or    cyano.-   R² very particularly preferably represents fluorine, chlorine,    bromine, iodine, methylthio, trifluoromethyl, trifluoromethoxy or    trifluoromethylthio,-   R³ very particularly preferably represents phenyl which is    optionally mono- to trisubstituted by identical or different    substituents, examples of substituents which may be mentioned being:    fluorine, chlorine, bromine, iodine, cyano, methyl, methoxy,    methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio    or trifluoromethylsulfonyl;

represents an oxadiazolyl group from the group consisting of:

where

-   X¹, X² and X³ independently of one another represent hydrogen,    C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio    and also represent phenyl or benzyl, each of which is optionally    mono- to trisubstituted by identical or different substituents from    the group consisting of halogen, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy    having in each case 1 to 3 identical or different halogen atoms from    the group consisting of fluorine, chlorine and bromine;

represents a tetrazolyl group from the group consisting of:

where

-   X⁴, X⁵, X⁶ and X⁷ independently of one another represent hydrogen,    C₁-C₄-alkyl, C₁-C₂-haloalkyl having 1 to 3 identical or different    halogen atoms from the group consisting of fluorine, chlorine and    bromine; C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, represent phenyl or    benzyl, each of which is optionally mono- to trisubstituted by    identical or different substituents from the group consisting of    halogen, C₁-C₂-haloalkyl and C₁-C₂-haloalkoxy having in each case 1    to 3 identical or different halogen atoms from the group consisting    of fluorine, chlorine and bromine; and also represent cyclopentyl or    cyclohexyl, each of which is optionally mono- to trisubstituted by    C₁-C₄-alkyl.-   R⁴ very particularly preferably represents hydrogen, cyanomethyl,    methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i-, s-    or t-butoxycarbonyl.-   R¹ especially preferably represents chlorine or cyano.-   R² especially preferably represents fluorine, chlorine, bromine,    iodine or trifluoromethylthio.-   R³ especially preferably represents phenyl which is optionally mono-    or disubstituted by identical or different substituents from the    group consisting of fluorine, chlorine, trifluoromethyl,    trifluoromethoxy and trifluoromethylthio;

represents an oxadiazolyl group from the group consisting of:

where

-   X¹, X² and X³ independently of one another represent hydrogen,    methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,    trifluoromethyl, trifluoromethoxy or trifluoromethylthio and also    represent phenyl or benzyl, each of which is optionally mono- or    disubstituted by identical or different substituents from the group    consisting of fluorine, chlorine, bromine, trifluoromethyl or    trifluoromethoxy;

represents a tetrazolyl group from the group consisting of:

where

-   X⁴, X⁵, X⁶ and X⁷ independently of one another represent hydrogen,    methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; fluoromethyl,    difluoromethyl, trifluoromethyl, 1,1-difluoroethyl,    2,2,2-trifluoroethyl, methylthio, ethylthio, methylsulfonyl,    ethylsulfonyl; represent phenyl or benzyl, each of which is    optionally mono- to disubstituted by identical or different    substituents from the group consisting of fluorine, chlorine,    bromine, methyl, methoxy, trifluoromethyl and trifluoromethoxy; and    also represent cyclohexyl which is optionally mono- to disubstituted    by methyl.-   R⁴ especially preferably represents hydrogen or cyanomethyl.

Preference is furthermore given to compounds of the formula (I) in whichR¹ represents cyano.

Preference is furthermore given to compounds of the formula (I) in whichR² represents halogen, preferably fluorine, chlorine, bromine, iodine,particularly preferably fluorine or chlorine, very particularlypreferably chlorine.

Preference is furthermore given to compounds of the formula (I) in whichR¹ represents cyano and R² represents chlorine.

Preference is furthermore given to compounds of the formula (I) in whichR⁴ represents hydrogen or cyanomethyl.

Preference is furthermore given to compounds of the formula (I) in whichR³ represents phenyl which is optionally mono- to trisubstituted byidentical or different substituents, examples of substituents which maybe mentioned being: fluorine, chlorine, bromine, iodine, cyano;C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, andalso represents C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthioor C₁-C₄-haloalkylsulfonyl having in each case 1 to 5 identical ordifferent halogen atoms from the group consisting of fluorine, chlorineand bromine; preferably represents phenyl which is optionally mono- totrisubstituted by identical or different substituents, examples ofsubstituents which may be mentioned being: fluorine, chlorine, bromine,iodine, cyano, methyl, methoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio or trifluoromethylsulfonyl;particularly preferably represents phenyl which is optionally mono- ordisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, trifluoromethyl, trifluoromethoxy andtrifluoromethylthio.

Preference is furthermore given to compounds of the formula (I) in whichR³ represents oxadiazolyl or thiadiazolyl, each of which is optionallymonosubstituted, examples of substituents which may be mentioned being:C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, and also phenyl or benzyl, each ofwhich is optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, C₁-C₄-haloalkyl andC₁-C₄-haloalkoxy;

preferably represents an oxadiazolyl group from the group consisting of:

where

-   X¹, X² and X³ independently of one another represent hydrogen,    C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio,    and also represent phenyl or benzyl, each of which is optionally    mono- to trisubstituted by identical or different substituents from    the group consisting of halogen, C₁-C₂-haloalkyl or C₁-C₂-haloalkoxy    having in each case 1 to 3 identical or different halogen atoms from    the group consisting of fluorine, chlorine and bromine;

particularly preferably represents an oxadiazolyl group from the groupconsisting of:

where

-   X¹, X² and X³ independently of one another represent hydrogen,    methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,    trifluoromethyl, trifluoromethoxy or trifluoromethylthio, and also    represent phenyl or benzyl, each of which is optionally mono- or    disubstituted by identical or different substituents from the group    consisting of fluorine, chlorine, bromine, trifluoromethyl and    trifluoromethoxy.

Preference is furthermore given to compounds of the formula (I) in whichR³ represents optionally substituted tetrazolyl, substituents which maybe mentioned being: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio,C₁-C₄-alkylsulfonyl, and also phenyl or benzyl, each of which isoptionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, C₁-C₄-haloalkyl andC₁-C₄-haloalkoxy, furthermore cyclopentyl or cyclohexyl, each of whichis optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of C₁-C₄-alkyl;

preferably represents a tetrazolyl group from the group consisting of:

where

-   X⁴, X⁵, X⁶ and X⁷ independently of one another represent hydrogen,    C₁-C₄-alkyl, C₁-C₂-haloalkyl having 1 to 3 identical or different    halogen atoms from the group consisting of fluorine, chlorine and    bromine; C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, represent phenyl or    benzyl, each of which is optionally mono- to trisubstituted by    identical or different substituents from the group consisting of    halogen, C₁-C₂-haloalkyl and C₁-C₂-haloalkoxy having in each case 1    to 3 identical or different halogen atoms from the group consisting    of fluorine, chlorine and bromine; and also represent cyclopentyl or    cyclohexyl, each of which is optionally mono- to trisubstituted by    C₁-C₄-alkyl;

particularly preferably represents a tetrazolyl group from the groupconsisting of:

where

-   X⁴, X⁵, X⁶ and X⁷ independently of one another represent hydrogen,    methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl; fluoromethyl,    difluoromethyl, trifluoromethyl, 1,1-difluoroethyl,    2,2,2-trifluoroethyl, methylthio, ethylthio, methylsulfonyl,    ethylsulfonyl; represent phenyl or benzyl, each of which is    optionally mono- to disubstituted by identical or different    substituents from the group consisting of fluorine, chlorine,    bromine, methyl, methoxy, trifluoromethyl and trifluoromethoxy; and    also represent cyclohexyl which is optionally mono- to disubstituted    by methyl.

The radical definitions or illustrations listed above or in preferredranges apply to the end products and correspondingly to startingmaterials and intermediates. These radical definitions can be combinedwith one another as desired, i.e. including combinations between therespective preferred ranges.

Preference according to the invention is given to the compounds of theformula (I) which contain a combination of the meanings listed above asbeing preferred (preferable).

Particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being particularly preferred.

Very particular preference according to the invention is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as being very particularly preferred.

Special preference according to the invention is given to the compoundsof the formula (I) which contain a combination of the meanings listedabove as being especially preferred.

In the radical definitions given above and below, hydrocarbon radicals,such as alkyl, are in each case straight-chain or branched as far asthis is possible—including in combination with heteroatoms such asalkoxy.

Using, for example,3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole and4-biphenyl isocyanate as starting materials, the course of the reactionof the process (a) according to the invention can be represented by theformula scheme below:

Using, for example,N-(4-phenyl)-3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-di-hydro-1-pyrazolecarboxanilideand bromacetonitrile as starting materials, the course of the reactionof the process (b) according to the invention can be represented by theformula scheme below:

Using, for example, 4-(5-tert-butyl-1,2,4-oxadiazol-3-yl)-aniline,triphosgene (bis(trichloromethyl) carbonate) and3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole asstarting materials, the course of the reaction of the process (c)according to the invention can be represented by the formula schemebelow:

The formula (II) provides a general definition of the pyrazolines to beused as starting materials for carrying out the processes (a) and (c)according to the invention. In this formula, R¹ and R² preferably,particularly preferably, very particularly preferably and especiallypreferably have those meanings which have already been mentioned inconnection with the description of the compounds of the formula (I)according to the invention as being preferred, particularly preferred,very particularly preferred and especially preferred for these radicals.

Some of the pyrazolines of the formula (II) are known (cf. for example,EP 0 438 690); some form part of the subject matter of DE 101 35 551(dated Jul. 20, 2001).

Pyrazolines of the formula (II) are obtained when substitutedacetophenones of the formula (VII)

in which

-   R¹ and R² are as defined above are, in a first step, reacted with    known bisdialkylaminomethanes of the formula (VIII)    (Alk)₂N—CH₂—N(Alk)₂  (VIII)    in which-   alk represents C₁-C₄-alkyl in the presence of an inert organic    solvent (preferably halogenated hydrocarbons, such as, for example,    methylene chloride or ethylene chloride) at temperatures between    0° C. and 120° C., preferably between 20° C. and 80° C. (cf., for    example, EP-A 0 546 420), and the resulting dialkylaminoalkyl    ketones of the formula (IX)    in which-   R¹, R² and Alk are as defined above are, if required, isolated and,    in a second step, reacted with hydrazine (hydrate) in the presence    of an inert organic solvent (preferably alcohols, such as, for    example, methanol or ethanol) at temperatures between 0° C. and 80°    C., preferably between 20° C. and 50° C. (cf. also the Preparation    Examples).

The substituted acetophenones of the formula (VII) are obtained whenhaloacetophenones of the formula (X)

in which

-   R² is as defined above and-   Hal² represents halogen are reacted with pyrazoles of the formula    (XI)    in which-   R¹ is as defined above in the presence of an inorganic or organic    base (for example potassium carbonate) and, if appropriate, in the    presence of an inert organic solvent (for example acetonitrile), at    temperatures between 0° C. and 100° C., preferably between 20° C.    and 80° C. (cf., for example, EP-A 0 438 690 and also the    Preparation Examples).

The haloacetophenones of the formula (X) and the pyrazoles of theformula (XI) are generally known compounds of organic chemistry and/orcan be obtained in a generally known manner.

The formula (III) provides a general definition of the isocyanatesfurther to be used as starting materials in the process (a) according tothe invention. In this formula, R³ preferably, particularly preferably,very particularly preferably and especially preferably has thosemeanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, very particularlypreferred and especially preferred for this radical.

The isocyanates of the formula (III) are generally known compounds oforganic chemistry and/or can be obtained in a generally known manner.

The formula (IV) provides a general definition of the halides to be usedas starting materials for carrying out the process (b) according to theinvention. In this formula, R⁴ preferably, particularly preferably, veryparticularly preferably and especially preferably has those meaningswhich have already been mentioned in connection with the description ofthe compounds of the formula (I) according to the invention as beingpreferred, particularly preferred, very particularly preferred andespecially preferred for this radical. Hal¹ preferably representschlorine or bromine.

The halides of the formula (IV) are generally known compounds of organicchemistry.

The formula (V) provides a general definition of the anilines to be usedas starting materials for carrying out the process (c) according to theinvention. In this formula, R³ and R⁴ preferably, particularlypreferably, very particularly preferably and especially preferably havethose meanings which have already been mentioned in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, particularly preferred, very particularlypreferred and especially preferred for these radicals.

Most of the anilines of the formula (V) are known (cf., for example,U.S. Pat. No. 3,270,029, U.S. Pat. No. 3,793,340, U.S. Pat. No.3,810,901, WO 97/14695, WO 98/28269, WO 98/50358, EP 0 155 507, EP 0 933581, DE 100 23 430; J. Med. Chem. 1978, 21, 1093-1100; Zh. Org. Khim.1976, 12, 1054-1057; Can. J. Chem. 1998, 76, 78-84 and J. Chem. Soc., C.Org. 1966, 840-845); some of them also form part of the subject matterof DE 101 39 721 (dated Aug. 13, 2001), and/or they can be obtained in aknown manner.

Thus, for example, the 4-(1,2,4-oxadiazol-3-yl)anilines of the formula(Va)

in which

-   X¹ is as defined above are obtained when 4-aminobenzamidoxime of the    formula (XII)    is reacted with an acylating agent of the formula (XIII)    X¹—CO-A  (XIII)    in which-   A represents a customary leaving group, such as, in particular,    chlorine, —OC₁-C₄-alkyl or —OCOX¹, and-   X¹ is as defined above, if appropriate in the presence of an inert    organic solvent (for example ethanol) and if appropriate in the    presence of a base (for example alkali metal alkoxides) at    temperatures between 20° C. and 120° C., preferably between 50° C.    and 100° C. (cf. also the Preparation Examples).

The 4-aminobenzamidoxime of the formula (XII) is obtained in a generallyknown manner when 4-cyanoaniline is reacted with hydroxylaminehydrochloride in the presence of a diluent, such as, preferably,aliphatic alcohols, and in the presence of a base (for example potassiumcarbonate) at temperatures between 20° C. and 120° C., preferablybetween 50° C. and 100° C.

Furthermore, for example, the 4-(1,2,4-oxadiazol-5-yl)anilines of theformula (Vb)

in which

-   X² is as defined above can be obtained when 4-aminobenzoic acid    esters of the formula (XIV)    in which-   alk¹ represents C₁-C₄-alkyl are reacted with amidoximes of the    formula (XV)    in which-   X² is as defined above, if appropriate in the presence of an inert    organic solvent (such as, preferably, aliphatic alcohols) and if    appropriate in the presence of a base (for example alkali metal    alkoxides) at temperatures between 20° C. and 120° C., preferably    between 50° C. and 100° C. (cf. also the Preparation Examples).

Furthermore, for example, 4-(tetrazol-5-yl)anilines of the formulae (Vc)and (Vd)

in which

-   X⁴ and X⁵ are as defined above can be obtained when    aminobenzonitrile of the formula (XVI)    is reacted with sodium azide and, for example, triethylamine    hydrochloride in the presence of an inert organic solvent (for    example acetonirile, dimethylformamide or toluene), preferably under    reflux, and the resulting tetrazoleanilines of the formula (V-A)    are, if appropriate, reacted with compounds of the formula (XVI)    E-X  (XVI)    in which-   X has the meanings given above for X⁴ and X⁵, except for hydrogen,    and-   E represents an anionic leaving group, such as, preferably,    chlorine, bromine, iodine, acetoxy, tosyl or mesyl, in the presence    of a diluent (for example acetonitrile or dimethylformamide) and, if    appropriate, in the presence of an acid acceptor (for example    potassium carbonate) at temperatures between 0° C. and 80° C.,    preferably between 20° C. and 50° C.

When preparing compounds in which X represents a tertiary alkyl radical,it is in some cases found to be advantageous to react the compounds ofthe formula (V-A) with tertiary alcohols in the presence of strong acids(for example trifluoroacetic acid and/or sulfuric acid) (cf. also thePreparation Examples).

Furthermore, for example, 4-(tetrazol-2-yl)anilines of the formula (Ve)

in which

-   X⁶ is as defined above can be obtained when    4-(tetrazol-2-yl)nitrobenzenes of the formula (XVII)    in which-   X⁶ is as defined above are reacted with customary reducing agents    (for example hydrazine hydrate), if appropriate in the presence of a    catalyst (for example iron(III) chloride) in the presence of an    inert organic solvent (for example methanol or tetrahydrofuran) at    temperatures between 50° C. and 120° C. (cf. also the Preparation    Examples).

The 4-(tetrazol-2-yl)nitrobenzenes of the formula (XVII) can beobtained, for example, when 4-fluoronitrobenzene of the formula (XVIII)

is reacted with tetrazoles of the formula (XIX)

in which

-   X⁶ is as defined above in a known manner, if appropriate in the    presence of an inert organic solvent (for example dimethylformamide)    and in the presence of a base (for example potassium carbonate) at    temperatures between 20° C. and 150° C., preferably between 50° C.    and 120° C. (cf. EP 0 884 311 and the Preparation Examples).

The process (a) according to the invention is preferably carried outusing diluents. Suitable diluents are virtually all inert organicsolvents. These preferably include aliphatic and aromatic, optionallyhalogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane,petroleum ether, benzine, ligroine, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether anddibutyl ether, methyl tert-butyl ether, methyl tert-amyl ether, glycoldimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane,ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketoneor methyl isobutyl ketone, esters, such as methyl acetate or ethylacetate, nitriles, such as, for example, acetonitrile or propionitrile,amides, such as, for example, dimethylformamide, dimethylacetamide andN-methylpyrrolidone, and also dimethyl sulfoxide, tetramethylene sulfoneor hexamethylphosphoric triamide.

The process (a) according to the invention is preferably also carriedout using a catalyst. Suitable catalysts are in particular tertiaryorganic amines, such as, for example, triethylamine.

In the process (a) according to the invention, the reaction temperaturescan be varied within a relatively wide range. In general, the process iscarried out at temperatures between 0° C. and 120° C., preferably attemperatures between 20° C. and 80° C.

The process (a) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to operateunder elevated or reduced pressure.

For carrying out the process (a) according to the invention, thestarting materials are generally employed in approximately equimolaramounts. However, it is also possible to use a relatively small excessof one of the two components employed. Work-up is carried out bycustomary methods (cf. the Preparation Examples).

The processes (b) and (c) according to the invention are preferablycarried out using diluents. Suitable diluents are virtually all inertorganic solvents. These preferably include aliphatic and aromatic,optionally halogenated hydrocarbons, such as pentane, hexane, heptane,cyclohexane, petroleum ether, benzine, ligroine, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such asdiethyl ether and dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone,methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone,esters, such as methyl acetate or ethyl acetate, nitriles, such as, forexample, acetonitrile or propionitrile, amides, such as, for example,dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and alsodimethyl sulfoxide, tetramethylene sulfone or hexamethylphosphorictriamide.

Suitable bases for carrying out the processes (b) and (c) according tothe invention are all acid binders which can be customarily employed forsuch reactions. Preference is given to using alkali metal and alkalineearth metal hydrides, such as lithium hydride, sodium hydride, potassiumhydride or calcium hydride; alkali metal and alkaline earth metalhydroxides, such as lithium hydroxide, sodium hydroxide, potassiumhydroxide or calcium hydroxide; alkali metal and alkaline earth metalcarbonates or bicarbonates, such as sodium carbonate or potassiumcarbonate or sodium bicarbonate or potassium bicarbonate or calciumcarbonate; alkali metal acetates, such as sodium acetate or potassiumacetate, alkali metal alkoxides, such as sodium tert-butoxide orpotassium tert-butoxide; furthermore basic nitrogen compounds, such astrimethylamine, triethylamine, tripropylamine, tributylamine,diisobutylamine, dicyclohexylamine, ethyldiisopropylamine,ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline,pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-,2-ethyl-, 4-ethyl- and 5-ethyl-2-methylpyridine,1,5-diazabicyclo[4.3.0]-non-5-ene (DBN),1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU),1,4-diazabicyclo[2.2.2]-octane (DABCO).

When carrying out the process (b) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between 0° C. and120° C., preferably at temperatures between 20° C. and 80° C.

The process (b) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to operateunder elevated or reduced pressure.

To carry out the process (b) according to the invention, the startingmaterials are generally employed in approximately equimolar amounts.However, it is also possible to use an excess of halide and base.Work-up is carried out by customary methods (cf the PreparationExamples).

When carrying out the process (c) according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, the process is carried out at temperatures between −10° C. and120° C., preferably at temperatures between 0° C. and 100° C.

The process (c) according to the invention is generally carried outunder atmospheric pressure. However, it is also possible to operateunder elevated or reduced pressure.

To carry out the process (c) according to the invention, the startingmaterials are generally employed in approximately equimolar amounts.However, it is also possible to use an excess of chloride and base.Work-up is carried out by customary methods (cf. the PreparationExamples).

The active compounds, having good plant tolerance and favorablewarm-blood toxicity, are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene sector. They may be preferably used ascrop protection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

-   From the order of the Isopoda, for example, Oniscus asellus,    Armadillidium vulgare and Porcellio scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus.-   From the order of the Chilopoda, for example, Geophilus carpophagus    and Scutigera spp.-   From the order of the Symphyla, for example, Scutigerella    immaculata.-   From the order of the Thysanura, for example, Lepisma saccharina.-   From the order of the Collembola, for example, Onychiurus armatus.-   From the order of the Orthoptera, for example, Acheta domesticus,    Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp.    and Schistocerca gregaria.-   From the order of the Blattaria, for example, Blatta orientalis,    Periplaneta americana, Leucophaea maderae and Blattella germanica.-   From the order of the Dermaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Reticulitermes spp.-   From the order of the Phthiraptera, for example, Pediculus humanus    corporis, Haematopinus spp., Linognathus spp., Trichodectes spp. and    Damalinia spp.-   From the order of the Thysanoptera, for example, Hercinothrips    femoralis, Thrips tabaci, Thrips palmi and Frankliniella    accidentalis.-   From the order of the Heteroptera, for example, Eurygaster spp.,    Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius    prolixus and Triatoma spp.-   From the order of the Homoptera, for example, Aleurodes brassicae,    Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,    Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi,    Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix,    Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli,    Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix    cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus,    Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,    Pseudococcus spp. and Psylla spp.-   From the order of the Lepidoptera, for example, Pectinophora    gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis    blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma    neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix    thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp.,    Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae,    Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa    pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia    kuehniella, Galleria mellonella, Tineola bisselliella, Tinea    pellionella, Hofinannophila pseudospretella, Cacoecia podana, Capua    reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona    magnanima, Tortrix viridana, Cnaphalocerus spp. and Oulema oryzae.-   From the order of the Coleoptera, for example, Anobium punctatum,    Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,    Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata,    Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala,    Epilachria varivestis, Atomaria spp., Oryzaephilus surinamensis,    Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,    Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,    Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp.,    Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus,    Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp.,    Conoderus spp., Melolontha melolontha, Amphimallon solstitialis,    Costelytra zealandica and Lissorhoptrus oryzophilus.-   From the order of the Hymenoptera, for example, Diprion spp.,    Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.-   From the order of the Diptera, for example, Aedes spp., Anopheles    spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.,    Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra    spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus    spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus,    Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis    capitata, Dacus oleae, Tipula paludosa, Hylemyia spp. and Liriomyza    spp.-   From the order of the Siphonaptera, for example, Xenopsylla cheopis    and Ceratophyllus spp.-   From the class of the Arachnida, for example, Scorpio maurus,    Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,    Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,    Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,    Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,    Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus    spp., Hemitarsonemus spp. and Brevipalpus spp.

The plant-parasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchusspp.

The compounds of the formula (I) according to the invention can beemployed with particularly good results for controlling plant-damaginginsects, such as, for example, against the larvae of the mustard beetle(Phaedon cochleariae) or the caterpillars of the army worm (Spodopterafrugiperda).

At certain concentrations or application rates, the compounds accordingto the invention may, if appropriate, also be used as herbicides andmicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they may also be used as intermediates or precursors forthe synthesis of further active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, inclusive of the transgenicplants and inclusive of the plant cultivars protectable or notprotectable by plant breeders' rights. Plant parts are to be understoodto mean all above-ground and underground parts and organs of plants,such as shoot, leaf, flower and root, examples which may be mentionedbeing leaves, needles, stalks, stems, flowers, fruit bodies, fruits,seeds, roots, tubers and rhizomes. The plant parts also includeharvested material, and vegetative and generative propagation material,for example cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and microencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants, and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics or chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulfoxide, and alsowater.

Suitable solid carriers are: for example ammonium salts and groundnatural minerals such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and silicates; suitablesolid carriers for granules are: for example crushed and fractionatednatural rocks such as calcite, marble, pumice, sepiolite and dolomite,and also synthetic granules of inorganic and organic meals, and granulesof organic material such as sawdust, coconut shells, maize cobs andtobacco stalks; suitable emulsifiers and/or foam-formers are: forexample nonionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates andalso protein hydrolysates; suitable dispersants are: for examplelignosulfite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in theirformulations, can also be used as a mixture with known fungicides,bactericides, acaricides, nematicides, or insecticides, for example towiden the spectrum of activity or to prevent the development ofresistance. In many cases, synergistic effects are achieved i.e., theefficacy of the mixture is greater than the efficacy of the individualcomponents.

Suitable mixing partners are, for example, the following compounds:

Fungicides:

aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril,benzamacryl-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate, calciumpolysulfide, carpropamide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb,dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos,dithianon, dodemorph, dodine, drazoxolon, ediphenphos, epoxiconazole,etaconazole, ethirimol, etridiazole, famoxadon, fenapanil, fenarimol,fenbuconazole, fenfuram, fenhexamide, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole,flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminum, fosetyl-sodium, fthalide, fuberidazole, furalaxyl,furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil,imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadinetriacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione,iprovalicarb, irumamycin, isoprothiolane, isovaledione, kasugamycin,kresoxim-methyl, copper preparations, such as: copper hydroxide, coppernaphthenate, copper oxychloride, copper sulfate, copper oxide,oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb,meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole,methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax,mildiomycin, myclobutanil, myclozolin, nickel dimethyldithiocarbamate,nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxolinicacid, oxycarboxim, oxyfenthiin, paclobutrazole, pefurazoate,penconazole, pencycuron, phosdiphen, picoxystrobin, pimaricin,piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone,propamocarb, propanosine-sodium, propiconazole, propineb,pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,pyroxyfur, quinconazole, quintozene (PCNB), quinoxyfen, sulfur andsulfur preparations, spiroxamines, tebuconazole, tecloftalam, tecnazene,teteyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamides,thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid,triadimefon, triadimenol, triazbutil, triazoxide, trichlamide,tricyclazole, tridemorph, trifloxystrobins, triflumizole, triforine,triticonazole, uniconazole, validamycin A, vinclozolin, viniconazole,zarilamide, zineb, ziram and also Dagger G, OK-8705, OK-8801, α-( 1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,(E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,1-[(diiodomethyl)-sulfonyl]-4-methyl-benzene,1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinol,2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole, 2-[(1-methylethyl)-sulfonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,2-aminobutane, ²-bromo-2-(bromomethyl)-pentanedinitrile,2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetarnide,2-phenylphenol (OPP),3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,3-(1,1-dimethylpropyl)-1-oxo-1H-indene-2-carbonitrile,3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide,4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one, 8-hydroxyquinolinesulfate, 9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,ethyl [(4-chlorophenyl)-azo]-cyanoacetate, potassium hydrogen carbonate,methanetetrathiol sodium salt, methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulfonamide,N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,N-(6-methoxy-3 -pyridinyl)-cyclopropanecarboxamide,N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,N-formyl-N-hydroxy-DL-alanine sodium salt, O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate, O-methylS-phenyl phenylpropylphosphoramidothioate, S-methyl1,2,3-benzothiadiazole-7-carbothioate,spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran-3′-one,4-[(3,4-dimethoxyphenyl)-3-(4-fluorophenyl)-acryloyl]-morpholine.

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulfate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin, AZ60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillusthuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella,bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,bifenazate, bifenthrin, bioethanomethrin, biopermethrin, bistrifluron,BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion,carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr,chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifosM, chlovaporthrin, chromafenozide, cis-resmethrin, cispermethrin,clocythrin, cloethocarb, clofentezine, clothianidine, cyanophos,cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,cypermethrin, cyromazine, deltamethrin, demeton M, demeton S,demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, dicofol,diflubenzuron, dimethoate, dimethylvinphos, diofenolan, disulfoton,docusat-sodium, dofenapyn, eflusilanate, emamectin, empenthrin,endosulfan, Entomopfthora spp., esfenvalerate, ethiofencarb, ethion,ethoprophos, etofenprox, etoxazole, etrimfos, fenamiphos, fenazaquin,fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb,fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate,fipronil, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate,flufenoxuron, flumethrin, flutenzine, fluvalinate, fonophos,fosmethilan, fosthiazate, fubfenprox, furathiocarb, granulosis viruses,halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene,imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,nuclear polyhedrosis viruses, lambda-cyhalothrin, lufenuron, malathion,mecarbam, metaldehyde, methamidophos, metharhizium anisopliae,metharhizium flavoviride, methidathion, methiocarb, methoprene,methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,milbemectin, milbemycin, monocrotophos, naled, nitenpyram, nithiazine,novaluron, omethoate, oxamyl, oxydemethon M, Paecilomyces fumosoroseus,parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M,profenofos, promecarb, propargite, propoxur, prothiofos, prothoate,pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben,pyridathion, pyrimidifen, pyriproxyfen, quinalphos, ribavirin,salithion, sebufos, silafluofen, spinosad, spirodiclofen, sulfotep,sulprofos, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,tetrachlorvinphos, tetradifon, thetacypermethrin, thiacloprid,thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate,thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin,triarathene, triazamate, triazophos, triazurone, trichlophenidine,trichlorfon, triflumuron, trimethacarb, vamidothion, vaniliprole,Verticillium lecanii, YI 5302, zeta-cypermethrin, zolaprofos,(1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,(3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, 1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,3-methylphenyl propylcarbamate,4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,Bacillus thuringiensis strain EG-2348, [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-ylbutanoate,[3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde, ethyl[2-[[1,6-dihydro-6-oxo-1-(phenyhnethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide, O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,N-cyanomethyl-4-trifluoromethyl-nicotinamide,3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)propoxy]-benzene.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators is also possible.

The active compounds according to the invention can furthermore bepresent when used as insecticides in their commercially availableformulations and in the use forms prepared from these formulations, as amixture with synergistic agents. Synergistic agents are compounds whichincrease the action of the active compounds, without it being necessaryfor the synergistic agent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (Genetic ModifiedOrganisms), and parts thereof a retreated. The term “parts” or “parts ofplants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. Plant cultivars are to be understood as meaning plants havingnovel properties (“traits”) which have been obtained by conventionalbreeding, by mutagenesis or by recombinant DNA techniques. This can bevarieties, bio- and genotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (i.e. those obtained by geneticengineering) which are preferably to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparted particularly advantageouslyuseful traits to these plants. Examples of such traits are better plantgrowth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, better quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products. Further and particularly emphasized examples ofsuch traits are a better defence of the plants against animal andmicrobial pests, such as against insects, mites, phytopathogenic fungi,bacteria and/or viruses, and also increased tolerance of the plants tocertain herbicidally active compounds. Examples of transgenic plantswhich may be mentioned are the important crop plants, such as cereals(wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape andalso fruit plants (with the fruits apples, pears, citrus fruits andgrapevines), and particular emphasis is given to maize, soya beans,potatoes, cotton and oilseed rape. Traits that are emphasized are inparticular increased defence of the plants against insects by toxinsformed in the plants, in particular those formed by the genetic materialfrom Bacillus thuringiensis (for example by the genes CryIA(a),CryLA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb andCryIF and also combinations thereof) in the plants (hereinbelow referredto as “Bt plants”). Traits that are also particularly emphasized are theincreased defence of the plants to fungi, bacteria and viruses bysystemic acquired resistance (SAR), systemin, phytoalexins, elicitorsand resistance genes and correspondingly expressed proteins and toxins.Traits that are furthermore particularly emphasized are the increasedtolerance of the plants to certain herbicidally active compounds, forexample imidazolinones, sulfonylureas, glyphosate or phosphinotricin(for example the “PAT” gene). The genes which impart the desired traitsin question can also be present in combination with one another in thetransgenic plants. Examples of “Bt plants” which may be mentioned aremaize varieties, cotton varieties, soya bean varieties and potatovarieties which are sold under the trade names YIELD GARD® (for examplemaize, cotton, soya beans), KnockOut® (for example maize), StarLink®(for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf®(potato). Examples of herbicide-tolerant plants which may be mentionedare maize varieties, cotton varieties and soya bean varieties which aresold under the trade names Roundup Ready® (tolerance to glyphosate, forexample maize, cotton, soya bean), Liberty Link® (tolerance tophosphinotricin, for example oilseed rape), IMI® (tolerance toimidazolinones) and STS® (tolerance to sulfonylureas, for examplemaize). Herbicide-resistant plants (plants bred in a conventional mannerfor herbicide tolerance) which may be mentioned also include thevarieties sold under the name Clearfield® (for example maize). Ofcourse, these statements also apply to plant cultivars having these orstill-to-be-developed genetic traits, which plants will be developedand/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants.

Particular emphasis is given to the treatment of plants with thecompounds or the mixtures specifically mentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

-   From the order of the Anoplurida, for example, Haematopinus spp.,    Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.-   From the order of the Mallophagida and the suborders Amblycerina and    Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton    spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina    spp., Trichodectes spp. and Felicola spp.-   From the order Diptera and the suborders Nematocerina and    Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,    Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,    Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp.,    Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca    spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp.,    Fannia spp., Glossina spp., Calliphora spp., Lucilia spp.,    Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp.,    Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.    and Melophagus spp.-   From the order of the Siphonapterida, for example, Pulex spp.,    Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.-   From the order of the Heteropterida, for example, Cimex spp.,    Triatoma spp., Rhodnius spp. and Panstrongylus spp.-   From the order of the Blattarida, for example, Blatta orientalis,    Periplaneta americana, Blattela germanica and Supella spp.-   From the subclass of the Acaria (Acarida) and the orders of the    Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp.,    Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,    Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus    spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,    Stemostoma spp. and Varroa spp.-   From the order of the Actinedida (Prostigmata) and Acaridida    (Astigmata), for example, Acarapis spp., Cheyletiella spp.,    Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,    Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,    Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,    Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,    Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injections(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of molded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) can be used as formulations (for example powders,emulsions, free-flowing compositions), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as beingpreferred—but without any limitation:

Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobiumpertinex, Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendronspec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec. and Dinoderus minutus.

Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigastaignus and Urocerus augur.

Termites, such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis and Coptotermes formosanus.

Bristletails, such as Lepisma saccharina.

Industrial materials in the present context are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentaccording to the invention or mixtures comprising this are to beunderstood as meaning, for example:

building timber, wooden beams, railway sleepers, bridge components, boatjetties, wooden vehicles, boxes, pallets, containers, telegraph poles,wood panelling, wooden windows and doors, plywood, chipboard, joinery orwooden products which are used quite generally in house-building or inbuilding joinery.

The active compounds can be used as such, in the form of concentrates orin generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyes and pigments, and also other processing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compound,based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., turpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin,silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odor correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or one drying vegetable oil.Alkyd resins having an oil content of more than 45% by weight,preferably 50 to 68% by weight, are preferably used according to theinvention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulfonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxideand triflumuron, and also fungicides, such as epoxyconazole,hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole,metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3 -one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with salt wateror brackish water, in particular hulls, screens, nets, buildings,moorings and signalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis-(trialkyltin) sulfides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulfide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combination with the antifoulingcompositions according to the invention are:

algicides such as2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,dichlorophen, diuron, endothal, fentin acetate, isoproturon,methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

fungicides such as benzo[b]thiophenecarboxylic acid cyclohexylamideS,S-dioxide, dichlofluanid, fluor-folpet, 3-iodo-2-propinylbutylcarbamate, tolylfluanid and azoles such as azaconazole,cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazoleand tebuconazole;

molluscicides such as fentin acetate, metaldehyde, methiocarb,niclosamid, thiodicarb and trimethacarb; or conventional antifoulingactive compounds such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one,diiodomethylparatryl sulfone,2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper,sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridine-triphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetra-methylthiuram disulfide and2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as rosin to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, inparticular insects, arachnids and mites, which are found in enclosedspaces such as, for example, dwellings, factory halls, offices, vehiclecabins and the like. They can be employed in domestic insecticideproducts for controlling these pests alone or in combination with otheractive compounds and auxiliaries. They are active against sensitive andresistant species and against all development stages. These pestsinclude:

-   From the order of the Scorpionidea, for example, Buthus occitanus.-   From the order of the Acarina, for example, Argas persicus, Argas    reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus    domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula    alfreddugesi, Neutrombicula autumnalis, Dermatophagoides    pteronissimus and Dermatophagoides forinae.-   From the order of the Araneae, for example, Aviculariidae and    Araneidae.-   From the order of the Opiliones, for example, Pseudoscorpiones    chelifer, Pseudoscorpiones cheiridium and Opiliones phalangium.-   From the order of the Isopoda, for example, Oniscus asellus and    Porcellio scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus    and Polydesmus spp.-   From the order of the Chilopoda, for example, Geophilus spp.-   From the order of the Zygentoma, for example, Ctenolepisma spp.,    Lepisma saccharina and Lepismodes inquilinus.-   From the order of the Blattaria, for example, Blatta orientalies,    Blattella germanica, Blattella asahinai, Leucophaea maderae,    Panchlora spp., Parcoblatta spp., Periplaneta australasiae,    Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa    and Supella longipalpa.-   From the order of the Saltatoria, for example, Acheta domesticus.-   From the order of the Dermaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Kalotermes spp. and    Reticulitermes spp.-   From the order of the Psocoptera, for example, Lepinatus spp. and    Liposcelis spp.-   From the order of the Coleptera, for example, Anthrenus spp.,    Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp.,    Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus    oryzae, Sitophilus zeamais and Stegobium paniceum.-   From the order of the Diptera, for example, Aedes aegypti, Aedes    albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora    erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex    pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca    domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp.,    Stomoxys calcitrans and Tipula paludosa.-   From the order of the Lepidoptera, for example, Achroia grisella,    Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea    pellionella and Tineola bisselliella.-   From the order of the Siphonaptera, for example, Ctenocephalides    canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans and    Xenopsylla cheopis.-   From the order of the Hymenoptera, for example, Camponotus    herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,    Monomorium pharaonis, Paravespula spp. and Tetramorium caespitum.-   From the order of the Anoplura, for example, Pediculus humanus    capitis, Pediculus humanus corporis and Phthirus pubis.-   From the order of the Heteroptera, for example, Cimex hemipterus,    Cimex lectularius, Rhodinus prolixus and Triatoma infestans.

They are used in the household insecticides sector alone or incombination with other suitable active compounds such as phosphoricesters, carbamates, pyrethroids, growth regulators or active compoundsfrom other known classes of insecticides.

They are used in aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The preparation and the use of the compounds according to the inventionis shown in the examples below.

PREPARATION EXAMPLES Example 1

(Process a)

At 70° C., 0.72 g (3.7 mmol) of 4-phenylphenyl isocyanate is added to amixture of 1 g (3.7 mmol) of 3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole, 0.1ml of triethylamine and 80 ml of methyl tert-amyl ether. The mixture isstirred at 70° C. for 15 minutes and then allowed to slowly cool to roomtemperature. The precipitated product is filtered off with suction andwashed with a little methyl tert-butyl ether.

This gives 1.2 g (69% of theory) ofN-(4-phenyl)-3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1-pyrazolecarboxanilideof logP (pH2)=4.11.Preparation of the Starting Material

At room temperature, 2.16 (0.021 mol) of bisdimethylaminomethane areadded to a solution of 5 g (0.02 mol) of2-(4-cyanopyrazol-1-yl)-4′-chloroacetophenone in 50 ml of methylenechloride, and the mixture is boiled under reflux for 18 hours. Thesolvent is then distilled off under reduced pressure and the residue isdissolved in 50 ml of ethanol. After addition of 1.13 g (0.0226 mol) ofhydrazine hydrate, the reaction mixture is stirred at 30° C. for 3hours. The precipitated product is filtered off with suction and washedwith a little cold ethanol and with water.

This gives 3.3 g (61% of theory) of3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole oflogP (pH2)=2.11.Preparation of the Precursor

A mixture of 9.3 g (0.04 mol) of 2-bromo-4′-chloroacetophenone, 3.9 g(0.042 mol) of 4-cyanopyrazole (preparation see JP H59-196868), 6.1 g(0.044 mol) of potassium carbonate and 50 ml of acetonitrile is stirredat room temperature overnight. About 200 ml of water are then added tothe reaction mixture and the precipitated product is filtered off withsuction and washed with water.

This gives 9.5 g (97% of theory) of2-(4-cyanopyrazol-1-yl)-4′-chloroacetophenone of logP (pH2)=2.20.

Example 2

(Process c)

At 0° C., a solution of 1.1 g (5 mmol) of4-(5-tert-butyl-[1,2,4]oxadiazol-3-yl)aniline and 0.7 ml (5 mmol) oftriethylamine in 25 ml of methylene chloride is added dropwise to asolution of 0.5 g (1.7 mmol) of triphosgene (bistrichloromethylcarbonate) in 50 ml of methylene chloride, and the mixture is stirred atroom temperature for half an hour. A solution of 1.36 (5 mmol) of3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole and0.7 ml (5 mmol) of triethylamine in 25 ml of methylene chloride is thenadded dropwise. The mixture is stirred at room temperature for 18 hoursand then washed twice with in each case 100 ml of water. The organicphase is dried over sodium sulfate and concentrated under reducedpressure. The residue is triturated with ethanol, filtered off withsuction and washed with ethanol.

This gives 0.6 g (23% of theory) ofN-[4-(5-tert-butyl[1.2.4]oxadiazol-3-yl)-phenyl]-3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1-pyrazolecarboxamideof logP (pH2)=4.33.Preparation of the Starting Material

A mixture of 4.5 g (0.03 mol) of 4-aminobenzamidoxime, 3.5 g (0.03 mol)of methyl pivalate, 50 ml of ethanol, 1 ml of a 28% strength sodiummethoxide solution in methanol and 2 g of molecular sieve 3 A is boiledunder reflux for 18 hours. The reaction mixture is then filtered and thefiltrate is concentrated under reduced pressure. Water is added to theresidue, and the precipitated crystals are then filtered off withsuction. The crude product is purified by silica gel chromatography(methylene chloride/diethyl ether 3:1).

This gives 2.1 g (33% of theory) of4-(5-tert-butyl[1,2,4]oxadiazol-3-yl)aniline in the form of colorlesscrystals of logP (pH2) of 2.31.

Example 3

(Process c)

At 0° C., a solution of 1.1 g (5 mmol) of4-(3-tert-butyl[1,2,4]oxadiazol-5-yl)aniline and 0.7 ml (5 mmol) oftriethylamine in 25 ml methylene chloride is added dropwise to asolution of 0.5 g ( 1.7 mmol) of triphosgene (bistrichloromethylcarbonate) in 50 ml of methylene chloride, and the mixture is stirred atroom temperature for half an hour. A solution of 1.36 g (5 mmol) of3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole and0.7 ml (5 mmol) of triethylamine in 25 ml of methylene chloride is thenadded dropwise. The mixture is stirred at room temperature for 18 hoursand then washed twice with in each case 100 ml of water. The organicphase is dried over sodium sulfate and concentrated under reducedpressure. The residue is triturated with ethanol, filtered off withsuction and washed with ethanol.

This gives 0.95 g (37% of theory) ofN-[4-(3-tert-butyl[1,2,4]oxadiazol-5-yl)-phenyl]-3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1-pyrazolecarbox-amideof logP (pH2)=4.38.Preparation of the Starting Material

A mixture of 6 g (0.04 mol) of methyl 4-aminobenzoate, 5.8 g (0.05 mol)of pival-amidoxime, 50 ml of ethanol, 1 ml of a 28% strength sodiummethoxide solution in methanol and 2 g of molecular sieve 3A is boiledunder reflux for 18 hours. Most of the solvent is then distilled offunder reduced pressure, the residue is cooled in an ice bath, a littlewater is added and the precipitated crystals are then filtered off withsuction. The crystals are washed with water and the residue is dissolvedin a solution of 4 g of potassium hydroxide in 50 ml of methanol. Thesolution is allowed to stand at room temperature for 3 days and thesolvent is then distilled off under reduced pressure. The residue istriturated with water and the precipitated product is filtered off withsuction and washed with water.

This gives 2.95 g (34% of theory) of4-(3-tert-butyl[1,2,4]oxadiazol-5-yl)aniline in the form of colorlesscrystals of logP (pH2) of 2.54.

Example 4

(Process c)

At 0° C., a solution of 0.64 g (3 mmol) of4-(2-tert-butyltetrazol-5-yl)aniline and 0.4 ml (3 mmol) oftriethylamine in 25 ml of methylene chloride is added dropwise to asolution of 0.35 g (1.2 mmol) of triphosgene (bistrichloromethylcarbonate) in 30 ml of methylene chloride, and the mixture is stirred atroom temperature for half an hour. A solution of 0.8 g (3 mmol) of3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole and0.4 ml (3 mmol) of triethylamine in 25 ml of methylene chloride is thenadded dropwise. The mixture is stirred at room temperature for 18 hoursand then washed twice with in each case 100 ml of water. The organicphase is dried over sodium sulfate and concentrated under reducedpressure. The residue is purified by silica gel chromatography(methylene chloride/diethyl ether 1:1).

This gives 0.3 g (19.5% of theory) ofN-[4-(2-tert-butyltetrazol-5-yl)phenyl]-3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1-pyrazolecarboxamideof logP (pH2)=3.91.Preparation of the Starting Material

3.8 ml of concentrated sulfuric acid are added to a mixture of 15 g(0.093 mol) of 5-(4-aminophenyl)tetrazole, 28 ml of tert-butanol and 80ml of trifluoroacetic acid. The reaction mixture is stirred for 16 hoursand the solvent is then distilled off under reduced pressure andsaturated sodium bicarbonate solution is added to the residue. Theproduct is extracted with ethyl acetate. The organic phase is dried oversodium sulfate and the solvent is then distilled off under reducedpressure.

What remains are 14.8 g (73% of theory) of4-(2-tert-butyltetrazol-5-yl)aniline in the form of beige crystals oflogP (pH2)=1.69.

Example 5

(Process c)

At 0° C., a solution of 1.2g (4.6 mmol) of3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1H-pyrazole and0.65 ml (4.6 mmol) of triethylamine in 25 ml of methylene chloride isadded dropwise to a solution of 0.45 g (1.54 mmol) of triphosgene(bistrichloromethyl carbonate) in 30 ml of methylene chloride, and themixture is stirred at room temperature for half an hour. A solution of 1g (4.6 mmol) of 4-(5-tert-butyltetrazol-2-yl)aniline and 0.65 ml (4.6mmol) of triethylamine in 25 ml of methylene chloride is then addeddropwise. The mixture is stirred at room temperature for 18 hours andthen washed twice with in each case 100 ml of water. The organic phaseis dried over sodium sulfate and concentrated under reduced pressure.The residue is purified by silica gel chromatography (methylenechloride/diethyl ether 1:1).

This gives 0.3 g (13% of theory) ofN-[4-(5-tert-butyltetrazol-2-yl)phenyl]-3-(4-chlorophenyl)-4-(4-cyanopyrazol-1-yl)-4,5-dihydro-1-pyrazolecarboxamideof logP (pH2)=4.27.Preparation of the Starting Material

At 75° C., 8.7 ml of hydrazine hydrate are added dropwise over a periodof two hours to a mixture of 12.7 g (0.051 mol) of4-(5-tert-butyltetrazol-2-yl)nitrobenzene, 1.5 g of activated carbon,0.3 g of iron(III) chloride, 20 ml of methanol and 100 ml oftetrahydrofuran. The mixture is then stirred at 75° C. overnight, cooledand filtered off with suction through kieselguhr, and the filter cake iswashed thoroughly with ethyl acetate. The filtrate is washed with sodiumchloride solution, dried and concentrated under reduced pressure.

This gives 15 g (quantitative) of 4-(5-tert-butyltetrazol-2-yl)anilineof logP (pH2)=2.27.Preparation of the Precursor

A mixture of 9.7 g (0.07 mol) of 4-fluoronitrobenzene, 8.7 g (0.7 mol)of 5-tert-butyltetrazole, 10.6 g (0.077 mol) of potassium carbonate and100 ml of dimethylformamide is stirred at 75° C. overnight. The reactionmixture is then cooled to room temperature and poured into 600 g ofice-water. The precipitated product is filtered off with suction andwashed with water.

This gives 12.7 g (73% of theory) of4-(5-tert-butyltetrazol-2-yl)nitrobenzene of logP (pH2)=2.20.

Analogously to Examples 1 to 5 and in accordance with the generalstatements on the preparation, it is possible to obtain the compounds ofthe formula (I) listed in Table 1 below: TABLE 1 (I)

No. R¹ R² R³ R⁴ logP (pH2) 6 CN Cl

H 4.31 7 CN Cl

H 2.93 8 CN Cl

H 3.49 9 CN Cl

H 3.10 10 CN Cl

CH₂CN 3.59 11 CN Cl

H 2.61 12 CN Cl

CH₂CN 4.00

Analogously to Examples 1 to 5 and in accordance with the generalstatements on the preparation, it is possible to obtain the compounds ofthe formula (II) listed in Table 2 below: TABLE 2 (II)

No. R¹ R² logP (pH2) 11-2 CN Br 2.20 11-3 CN I 2.33 11-4 CN SCF₃ 2.78

Analogously to Example 1 and in accordance with the general statementson the preparation, it is possible to obtain the precursors of theformula (VII) listed in Table 3: TABLE 3 (VII)

No. R¹ R² logP (pH2) (VII)-2 CN Br 2.31 (VII)-3 CN I 2.47 (VII)-4 CNSCF₃ 2.91

The logP values given in the Preparation Examples and the tables aboveare determined in accordance with EEC Directive 79/831 Annex V.A8 byHPLC (High Performance Liquid Chromatography) on a reversed-phase column(C 18). Temperature: 43° C.

The determination is carried out in the acidic range at pH 2.3 using themobile phases 0.1% aqueous phosphoric acid and acetonitrile; lineargradient from 10% acetonitrile to 90% acetonitrile.

Calibration is carried out using unbranched alkan-2-ones (having 3 to 16carbon atoms) with known logP values (determination of the logP valuesby the retention times using linear interpolation between two successivealkanones).

Use Examples Example A

Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilethe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,for example, the compounds 2, 4, 6, 7 and 9 of the Preparation Examplesshow a kill of 100% after 7 days.

Example B

Spodoptera Frugiperda Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the army worm (Spodoptera frugiperda)while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

In this test, at an exemplary active compound concentration of 500 ppm,for example, the compounds 1, 2, 3, 4 and 9 of the Preparation Examplesshow a kill of 100% after 7 days.

Example C

Diabrotica Balteata Test (Larvae in Soil)

Critical concentration test/soil insects—treatment of transgenic plants

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil. Here, theconcentration of active compound in the preparation is virtuallyimmaterial, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled in0.25 1 pots, and these are allowed to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of thecultivar YIELD GUARD (trade mark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the appropriate test insects are placed into thetreated soil. After a further 7 days, the efficacy of the activecompound is determined by counting the maize plants that have emerged (1plant=20% activity).

Example D

Heliothis Virescens Test (Treatment of Transgenic Plants)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trade markof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and are populated withthe tobacco budworm Heliothis virescens while the leaves are stillmoist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars have been killed.

1-14. (canceled)
 15. A substituted pyrazoline of formula (I)

or isomers or isomer mixtures thereof, in which R¹ represents halogen orcyano, R² represents halogen, haloalkyl, alkoxy, haloalkoxy, alkylthio,haloalkylthio, alkylsulfonyl, haloalkylsulfinyl, haloalkylsulfonyl, orcyano, R³ represents optionally substituted aryl or optionallysubstituted hetaryl, and R⁴ represents hydrogen, cyanomethyl, oralkoxycarbonyl.
 16. A substituted pyrazoline of formula (I) as claimedin claim 15 in which R¹ represents fluorine, chlorine, bromine, iodine,or cyano, R² represents fluorine, chlorine, bromine, iodine,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfinyl,C₁-C₄-haloalkylsulfonyl, or cyano, R³ represents aryl that is optionallymono- or polysubstituted by identical or different substituents selectedfrom the group consisting of halogen, alkyl, alkoxy, alkylthio,alkylsulfonyl, haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfonyland cyano; represents optionally monosubstituted oxadiazolyl orthiadiazolyl, wherein the substituent is optionally substituted alkyl,optionally substituted alkoxy, optionally substituted alkylthio,optionally substituted aryl, or optionally substituted arylalkyl; orrepresents optionally monosubstituted tetrazolyl, wherein thesubstituent is optionally substituted alkyl, optionally substitutedalkylthio or alkylsulfonyl, optionally substituted aryl or arylalkyl, oroptionally substituted cycloalkyl, and R⁴ represents hydrogen,cyanomethyl or C₁-C₄-alkoxycarbonyl.
 17. A substituted pyrazoline offormula (I) as claimed in claim 15 in which R¹ represents chlorine,bromine, iodine, or cyano, R² represents fluorine, chlorine, bromine,iodine, cyano, C₁-C₂-alkylthio, or C₁-C₂-alkylsulfonyl; or representsC₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, C₁-C₂-haloalkylthio, orC₁-C₂-haloalkylsulfonyl having in each case 1 to 5 identical ordifferent halogen atoms selected from the group consisting of fluorine,chlorine, and bromine, R³ represents phenyl that is optionally mono- totrisubstituted by identical or different substituents, wherein thesubstituents are fluorine, chlorine, bromine, iodine, cyano,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, or C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, orC₁-C₄-haloalkylsulfonyl having in each case 1 to 5 identical ordifferent halogen atoms selected from the group consisting of fluorine,chlorine, and bromine; represents optionally monosubstituted oxadiazolylor thiadiazolyl, wherein the substituents are 4-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, or C₁-C₄-haloalkylthio;represents phenyl or benzyl, each of which is optionally mono- totrisubstituted by identical or different substituents selected from thegroup consisting of halogen, C₁-C₄-haloalkyl, and C₁-C₄ haloalkoxy;represents optionally substituted tetrazolyl, wherein the substituentsare C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl;represents phenyl or benzyl, each of which is optionally mono- totrisubstituted by identical or different substituents selected from thegroup consisting of halogen, C₁-C₄-haloalkyl, and C₁-C₄-haloalkoxy; orrepresents cyclopentyl or cyclohexyl, each of which is optionally mono-to trisubstituted by identical or different substituents selected fromthe group consisting of C₁-C₄-alkyl, and R⁴ represents hydrogen,cyanomethyl or C₁-C₄-alkoxycarbonyl.
 18. A substituted pyrazoline offormula (I) as claimed in claim 15 in which R¹ represents chlorine,bromine, or cyano, R² represents fluorine, chlorine, bromine, iodine,methylthio, trifluoromethyl, trifluoromethoxy, or trifluoromethylthio,R³ represents phenyl that is optionally mono- to trisubstituted byidentical or different substituents, wherein the substituents arefluorine, chlorine, bromine, iodine, cyano, methyl, methoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio ortrifluoromethylsulfonyl; represents an oxadiazolyl group selected fromthe group consisting of

where X¹, X², and X³ independently of one another represent hydrogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, or C₁ -C₄-haloalkylthio;or phenyl or benzyl, each of which is optionally mono- to trisubstitutedby identical or different substituents selected from the groupconsisting of halogen, C₁-C₂-haloalkyl, and C₁ -C₂-haloalkoxy having ineach case 1 to 3 identical or different halogen atoms selected from thegroup consisting of fluorine, chlorine, and bromine; or represents atetrazolyl group selected from the group consisting of:

where X⁴, X⁵, X⁶, and X⁷ independently of one another representhydrogen, C₁-C₄-alkyl, C₁-C₂-haloalkyl having 1 to 3 identical ordifferent halogen atoms selected from the group consisting of fluorine,chlorine, and bromine; C₁-C₄-alkylthio; C₁-C₄-alkylsulfonyl; phenyl orbenzyl, each of which is optionally mono- to trisubstituted by identicalor different substituents selected from the group consisting of halogen,C₁-C₂-haloalkyl, and C₁-C₂-haloalkoxy having in each case 1 to 3identical or different halogen atoms selected from the group consistingof fluorine, chlorine; and bromine; or cyclopentyl or cyclohexyl, eachof which is optionally mono- to trisubstituted by C₁-C₄-alkyl, and R⁴represents hydrogen, cyanomethyl, methoxycarbonyl, ethoxycarbonyl, n- ori-propoxycarbonyl, or n-, i-, s-, or t-butoxycarbonyl.
 19. A substitutedpyrazoline of formula (I) as claimed in claim 15 in which R¹ representschlorine or cyano, R² represents fluorine, chlorine, bromine, iodine, ortrifluoromethylthio, R³ represents phenyl that is optionally mono- ordisubstituted by identical or different substituents selected from thegroup consisting of fluorine, chlorine, trifluoromethyl,trifluoromethoxy, and trifluoromethylthio; represents an oxadiazolylgroup selected from the group consisting of:

where X¹, X² and X³ independently of one another represent hydrogen,methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, trifluoromethyl,trifluoromethoxy, or trifluoromethylthio; or phenyl or benzyl, each ofwhich is optionally mono- or disubstituted by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, trifluoromethyl, and trifluoromethoxy; represents a tetrazolylgroup selected from the group consisting of:

where X⁴, X⁵, X⁶ and X⁷ independently of one another represent hydrogen,methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, fluoromethyl,difluoromethyl, trifluoromethyl, 1,1-difluoroethyl,2,2,2-trifluoroethyl, methylthio, ethylthio, methylsulfonyl, orethylsulfonyl; phenyl or benzyl, each of which is optionally mono- todisubstituted by identical or different substituents selected from thegroup consisting of fluorine, chlorine, bromine, methyl, methoxy,trifluoromethyl, and trifluoromethoxy; or cyclohexyl that is optionallymono- to disubstituted by methyl, and R⁴ represents hydrogen orcyanomethyl.
 20. A substituted pyrazoline of formula (I) as claimed inclaim 15 in which R¹ is cyano.
 21. A substituted pyrazoline of formula(I) as claimed in claim 15 in which R² is halogen.
 22. A substitutedpyrazoline of formula (I) as claimed in claim 15 in which R² isfluorine, chlorine, bromine, or iodine.
 23. A substituted pyrazoline offormula (I) as claimed in claim 15 in which R¹ is cyano and R² ischlorine.
 24. A substituted pyrazoline of formula (I) as claimed inclaim 15 in which R⁴ is hydrogen or cyanomethyl.
 25. A process forpreparing substituted pyrazolines of formula (I) as claimed in claim 15comprising (a) reacting a pyrazoline of formula (II)

or isomers or isomer mixtures thereof, in which R¹ and R² are as definedfor formula (I) in claim 15, with an isocyanate of formula (III)

or isomers or isomer mixtures thereof, in which R³ is as defined forformula (I) in claim 15, optionally in the presence of a diluent andoptionally in the presence of a catalyst, to form a pyrazolinederivative of formula (la) according to the invention

or isomers or isomer mixtures thereof, in which R¹, R², and R³ are asdefined for formula (I) in claim 15, and, optionally, (b) reacting thepyrazoline derivative of formula (Ia) with a halide of formula (IV)Hal¹-R⁴  (IV) or isomers or isomer mixtures thereof, in which R⁴ is asdefined for formula (I) in claim 15, and Hal¹ represents halogen,optionally in the presence of a diluent and optionally in the presenceof a base; or (c) initially reacting an aniline of formula (V)

or isomers or isomer mixtures thereof, in which R³ and R⁴ are as definedfor formula (I) in claim 15, with phosgene in the presence of a diluentand optionally in the presence of a base, to form a carbamoyl chlorideof formula (VI)

or isomers or isomer mixtures thereof, in which R³ and R⁴ are as definedfor formula (I) in claim 15, and reacting the carbamoyl chloride offormula (VI), directly or after intermediate isolation, with apyrazoline of formula (II)

or isomers or isomer mixtures thereof, in which R¹ and R² are as definedfor formula (I) in claim 15, in the presence of a diluent and optionallyin the presence of a base.
 26. A pesticide comprising one or morecompounds of formula (I) as claimed in claim 15 and one or moreextenders and/or surfactants.
 27. A method of controlling pestscomprising allowing an effective amount of a compound of formula (I) asclaimed in claim 15 to act on pests and/or their habitat.
 28. A processfor preparing a pesticide comprising mixing a compound of formula (I) asclaimed in claim 15 with one or more extenders and/or surfactants.